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Circular Dichroism of a Chiral Tethered DonorЦAcceptor System Enhanced Anisotropy Factors in Charge-Transfer Transitions by Dimer Formation and by Confinement.

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mechanisms and also in the development of molecular
devices, such as nonlinear optical materials.[4] Chiral CT
interaction is expected to be a useful tool not only for
developing unique chiral molecular devices, but also for
understanding and controlling molecular recognition phenomena, especially in solution. Therefore, optical rotatory
dispersion and circular dichroism of optically active donor–
acceptor complexes have already been examined for CT
complexes that involve n–p* transitions.[5] Herein, we report
the circular dichroism of intra- and intermolecular CT
complexes with p–p* transitions, and also novel strategies
for controlling the anisotropy factor by dimer formation and
by confinement.
We chose 2,6-dimethoxynaphthalene and 4-cyano-Nmethylpyridinium as a donor–acceptor pair, since these
compounds possess low oxidation and reduction potentials
(Eox = 1.1–1.3 and Ered = 0.64 V versus the saturated calomel
electrode (SCE), respectively)[6] and are expected to form a
strong CT complex in solution. By linking these components
with a trimethylene tether, we obtained CT dyad 1 as the BF4
salt, which was then subjected to electronic absorption (UV/
Vis) and circular dichroism (CD) spectroscopy to study the
CT complexation behavior and to elucidate the chiroptical
properties of the representative CT complex(es) formed
under a variety of conditions (Scheme 1).
Donor–Acceptor Systems
Circular Dichroism of a Chiral Tethered Donor–
Acceptor System: Enhanced Anisotropy Factors
in Charge-Transfer Transitions by Dimer
Formation and by Confinement**
Tadashi Mori* and Yoshihisa Inoue*
Charge-transfer (CT) interactions between a donor and an
acceptor[1] are an important class of weak interactions that
have been extensively exploited in molecular assemblies such
as rotaxanes, catenanes, and molecular machines and devices.[2] A large number of tethered donor–acceptor pairs, or CT
dyads, have been prepared[3] in the study of electron-transfer
[*] Dr. T. Mori
Department of Molecular Chemistry
Graduate School of Engineering, Osaka University
2-1 Yamada-oka, Suita 565-0871 (Japan)
Fax: (+ 81) 6-6879-7923
Prof. Dr. Y. Inoue
The Entropy Control Project
4-6-3 Kamishinden, Toyonaka 560-0085 (Japan)
Fax: (+ 81) 6-6836-1636
[**] Financial support of this work by a Grant-in-Aid for Scientific
Research from the Ministry of Education, Culture, Sports, Science,
and Technology of Japan (No. 16750034, to T.M.) is gratefully
Supporting information for this article is available on the WWW
under or from the author.
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Scheme 1. Modes of CT complexation of the tethered chiral donor–
acceptor dyad 1.
The UV/Vis spectrum of dyad 1, measured in dichloromethane at 25 8C, was almost superimposable on a sum of the
spectra of the component donor and acceptor units, but
exhibited a very weak band at 420 nm, which is assigned to a
CT transition. An independent spectral titration of the
intermolecular complex formation of 4-cyano-N-methylpyridinium with 2,6-dimethoxynaphthalene at varying concentrations also gave a CT band at comparative wavelengths. A
Benesi–Hildebrand analysis[7] of the spectral titration results
indicates the formation of a 1:1 complex with an association
constant (KCT = 0.48 m 1) and spectral properties (lmax =
420 nm, eCT = 450 m 1 cm1) comparable to those reported
for analogous nonchiral donor–acceptor pairs.[8] In contrast,
the intensity of the CT band of 1 was linearly proportional to
the concentration of 1 (at least up to 10 mm), which
unequivocally indicated the intramolecular character of the
CT complex observed. A face-to-face stacked complex with a
DOI: 10.1002/anie.200462071
Angew. Chem. Int. Ed. 2005, 44, 2582 –2585
folded structure (Scheme 1, folded monomer A) is probably
formed upon the intramolecular CT interaction of 1, as judged
from the ROESY spectrum of 1 in CD2Cl2 at 25 8C (see the
Supporting Information). A similar conformation was
reported for the intermolecular CT complex of 2,6dimethoxynaphthalene with methyl viologen in an X-ray
crystallographic study.[9]
The UV/Vis spectrum of 1 showed a dramatic temperature dependence, particularly at temperatures lower than
50 8C; as the temperature decreased, a CT band at 480 nm
became apparent. The dependency of the absorbance of the
CT band on concentration (Figure 1), as well as the DFT
CD spectroscopy was also performed to elucidate the
effects of the different conformation and association states
A–C (Scheme 1) on the chiroptical properties of dyad 1. A
solution of 1 in dichloromethane (1 mm) showed only a weak
positive CD for the 1Lb transition of the naphthalene moiety
at around 320 nm (Figure 3, trace a), which is in good
agreement with the well-documented benzene sector rule.[11]
The obtained g factor is extremely small, as low as 8 105.
However, this seems reasonable for such a chromophore that
carries the smallest chiral auxiliary attached through a flexible
ether linkage. Furthermore, no appreciable CT band was
observed under the conditions employed. We may conclude,
Figure 1. Experimental (*) and theoretical (c) concentration
dependence of the absorbance of the CT band (at 480 nm) of dyad 1
in dichloromethane at 95 8C. The nonlinear least-squares fit revealed
the dimeric nature of the CT complexation (K = 3160 m1).
calculations[10] (Figure 2), indicate that the origin of this CT
band is the formation of an intermolecular 1:1 dimer in a
head-to-tail orientation, in which two sets of donor–acceptor
interactions are involved (Scheme 1, dimer C).
Figure 2. DFT-optimized structures of dimeric and monomeric dyad 1.
All calculations were performed with the Gaussian 98 package at the
B3LYP/6-31G(d) level. Hydrogen atoms are omitted for clarity.
Angew. Chem. Int. Ed. 2005, 44, 2582 –2585
Figure 3. Anisotropy (g) factor profiles of 1 under different conditions:
a) 1 mm in CH2Cl2 at 25 8C; b) 10 mm in MeCN at 25 8C; c) 1 mm in
CH2Cl2 at 95 8C (intensities corrected for the actual concentration of
dimeric species: 0.34 mm); d) 1 mm in MeOH at 25 8C, for comparison with (e) and (f); e) 1 mm in water containing 5 mm b-cyclodextrin
at 25 8C; f) 1 mm in water containing 5 mm g-cyclodextrin at 25 8C.
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
therefore, that extended monomer B is the dominant species
at a concentration of 1 mm at 25 8C.
At a higher concentration (10 mm in acetonitrile), the CD
spectral behavior of 1 changed significantly; a very weak CD
was observed in the 1Lb region (300–350 nm) and an apparent
negative CD in the CT transition region (Figure 3, trace b).
Although we employed acetonitrile as the solvent of choice
because of the lower solubility of 1 in less polar solvents, we
have not observed so far a notable solvent dependence on the
CD spectra of 1. The contribution of the intramolecular CT
complex A is probably enhanced to some extent under these
conditions. The formation of the dimeric CT complex C was
greatly promoted by reducing the temperature. Thus, a
solution of 1 in dichloromethane (1 mm) exhibited a strong
CD at 400–500 nm at 95 8C, along with a moderate CD in
the 1Lb region. As can be seen from Figure 3, trace c, the
g factor reaches 0.0016 for the CT band (dimer B) and
0.0005–0.001 even at the shorter wavelengths. These values
are at least one order of magnitude larger than the representative values reported for typical allowed transitions.[11]
The anomalous g factors may be attributed to the conformational fixation caused by stronger interactions in the dimeric
CT complex (see below).
The effects of conformational fixation caused by confinement on the chiroptical properties of the CT complex were
further investigated by supramolecular interaction with cyclodextrin hosts. The host–guest interactions of 1 with cyclodextrins were first assessed by fluorescence spectroscopy. As
can be seen from Figure 4, a solution of 1 in methanol
(0.1 mm) showed fairly weak fluorescence at 330 nm (trace a)
because of efficient intramolecular electron-transfer quenching, whereas much more intense fluorescence was observed
upon the addition of b- or g-cyclodextrin (0.5 mm) to an
aqueous solution of 1 (0.1 mm ; traces b and c). Similar
behavior was previously reported for a variety of aromatic
donor–viologen systems.[12] The fluorescent donor group is
included in the cavity of b-cyclodextrin, so both intra- and
intermolecular quenching by the pyridinium moiety and
solvent molecules are greatly decelerated and the excited
state is retained longer. In contrast, fluorescence enhancement is moderate in the case of g-cyclodextrin (Figure 4,
trace c). This result may be rationalized by a loose fitting of
the donor group to a larger g-cyclodextrin cavity, which can
not completely prevent the quenching attack of the pyridinium moiety or solvent molecules. 1H NMR spectroscopic
analysis of the complexes also supports this conclusion, as the
aromatic protons are much more deshielded in the presence
of b-cyclodextrin than in the presence of g-cyclodextrin (see
the Supporting Information).
Upon the addition of b- or g-cyclodextrin (5 mm) to an
aqueous solution of 1 (1 mm), large negative Cotton effects
were induced in the 1Lb ( 340 nm) and 1La ( 240 nm)
regions of the naphthalene chromophore (Figure 3, traces e
and f). This result is consistent with the empirical rules[13] and
indicates that the longer axis of the naphthalene moiety is
parallel to the axis of the cyclodextrin cavity. Interestingly, the
CT band exhibited larger negative Cotton effects with
unusually large g factors of 0.00028 and 0.00008 for the
b- and g-cyclodextrin complexes, respectively. The strong CD
for the CT band, particularly in the presence of b-cyclodextrin, is quite puzzling, since the cavity is formally fitted to
the size of naphthalene and the included naphthalene moiety
does not appear to form a CT complex even with the tethered
pyridinium moiety. By combining all the results from the UV/
Vis, fluorescence, NMR, and CD spectral examinations, we
tentatively rationalize this interesting chiroptical behavior of
the b-cyclodextrin complex of 1 as being a consequence of a
shallow penetration or perching of the acceptor moiety into
the b-cyclodextrin cavity, which is already occupied by the
more hydrophobic naphthalene moiety, to afford a less faceto-face, twisted CT complex. It is thus inferred that the
naphthalene moiety is accommodated in the b-cyclodextrin
cavity and the remaining acceptor moiety is forced to form a
tilted CT complex, which is closely located and/or twisted
relative to the donor moiety and hence exhibits a stronger
Cotton effect. However, the donor–acceptor pair is more
face-to-face and less tightly packed in a larger g-cyclodextrin
cavity, which results in a less intense Cotton effect.
As formulated by Hush (mostly for transition-metal
complexes), the electronic coupling element (Hab) is related
to the charge-transfer transition according to Equation (1),[14]
H ab ½cm1 ¼ 0:0206ðnmax Dn1=2 eÞ1=2 =r
Figure 4. Fluorescence emission and excitation spectra of 1 (0.1 mm)
at ambient temperature: a) in methanol (ten times expansion); in the
presence of b) b- and c) g-cyclodextrin (0.5 mm) in water.
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
in which nmax and Dn1/2 are the peak position and full width at
half maximum (in wavenumbers) of the CT band, e is the
molar extinction coefficient at the CT-band maxima, and r is
the effective separation of relevant redox centers in the
complex.[15] The electronic coupling element Hab was estimated for the CT transition of 1 under various conditions to
give the values listed in Table 1. Notably, the CT interaction in
the dimer is almost twice as large as that in the monomer. The
Hab value for the b-cyclodextrin complex is also appreciably
larger than that of the uncomplexed monomer, probably as a
result of the stronger intramolecular donor–acceptor interactions of 1 within the hydrophobic cyclodextrin cavities, or a
slightly larger separation between donor and acceptor.
Angew. Chem. Int. Ed. 2005, 44, 2582 –2585
Table 1: Anisotropy (g) factors and electronic coupling elements (Hab) of
monomeric and dimeric CT complexes and the b-cyclodextrin inclusion
CT species Conditions
Hab[a] lmax[b] g factor [ 103]
[1] = 10 mm in MeCN, 25 8C 0.65
[1] = 1 mm in water, 25 8C
[1] = 1 mm in CH2Cl2, 95 8C 1.23
[a] Electronic coupling element [103 cm1], calculated by the Marcus–
Hush equation [Eq. (1)], with the assumtion r = 3.5 . [b] Absorption
maximum of the CT band [nm].
It has thus been demonstrated for the first time that
donor–acceptor dyads, such as 1, form both intramolecular
monomeric and intermolecular dimeric CT complexes
depending on the conditions employed, and that their CT
bands give anomalously large g factors of up to 0.002. Such an
enhancement in g factor upon CT interaction is of theoretical/
mechanistic interest and also of practical use as a tool for
enhancing the efficiency of absolute asymmetric synthesis
with circularly polarized light.[16]
Received: September 22, 2004
Revised: January 21, 2005
Published online: March 22, 2005
Keywords: anisotropy · charge transfer · circular dichroism ·
cyclodextrins · donor–acceptor systems
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2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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circular, dimer, formation, donorцacceptor, tethered, system, transitional, chiral, factors, dichroism, confinement, transfer, enhance, anisotropic, charge
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